CN110607102A - Polyacrylic acid/metal colloid particle film forming material and preparation method and application thereof - Google Patents
Polyacrylic acid/metal colloid particle film forming material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110607102A CN110607102A CN201910934469.5A CN201910934469A CN110607102A CN 110607102 A CN110607102 A CN 110607102A CN 201910934469 A CN201910934469 A CN 201910934469A CN 110607102 A CN110607102 A CN 110607102A
- Authority
- CN
- China
- Prior art keywords
- polyacrylic acid
- metal
- forming material
- particle film
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention belongs to the technical field of material synthesis and metal surface pretreatment, and particularly relates to a polyacrylic acid/metal colloid particle film-forming material, and a preparation method and application thereof; according to the invention, polyacrylic acid can be ionized to generate a large amount of-COO-groups by adjusting the pH value of a polyacrylic acid solution, the-COO-groups can react with gradually added metal cations through electrostatic adsorption to form polyacrylic acid/metal aggregates, the aggregates formed preliminarily can be further assembled with the reaction to finally form polyacrylic acid/metal colloid particles, and the polyacrylic acid film-forming material doped with the polyacrylic acid/metal colloid particles can be obtained uniformly and stably by controlling the reaction conditions; according to the invention, by using a technical means of doping colloidal particles, the polyacrylic acid/metal colloidal particle film forming material is synthesized in situ, the film forming property of polyacrylic acid is effectively improved through nano modification, the quality of a formed pretreatment film layer is improved, and the adhesive force and the corrosion resistance of the film layer are improved.
Description
Technical Field
The invention belongs to the technical field of material synthesis and metal surface pretreatment, and particularly relates to a polyacrylic acid/metal colloid particle film-forming material, and a preparation method and application thereof.
Background
The most widely applied pretreatment technology in the field of metal coating pretreatment is the phosphating technology, but the phosphating technology is limited in use because a large amount of waste liquid containing phosphorus, heavy metal and nitrite and sediments are generated in the using process to cause environmental pollution. At present, common alternative technologies mainly comprise an inorganic oxide film forming technology and an organic self-assembly film forming technology, but the film prepared by the two technologies has a thin and smooth film layer, so that the surface roughness is small, and further, the paint film adhesion performance and the corrosion resistance performance of the paint film have obvious differences from the traditional phosphating technology. This directly limits the widespread use of these two techniques in the field of metal surface treatment. Therefore, the development of an environment-friendly metal surface treatment material with excellent performance and a treatment technology to replace the traditional phosphating technology widely used at present has important social benefits and economic values and is imperative. Therefore, the invention discloses a preparation method of a novel polyacrylic acid-based metal surface pretreatment material, a pretreatment film layer formed on the surface of a steel material by using the film-forming material prepared by the method has higher surface roughness and thicker film layer thickness, and the adhesion and the corrosion resistance of the pretreatment film layer can be obviously improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a polyacrylic acid/metal colloid particle film forming material and a preparation method thereof, and prepares an environment-friendly chemical conversion film with excellent performance on the surface of steel by using the material.
The preparation method of the polyacrylic acid/metal colloid particle film-forming material comprises the following steps:
(1) preparing polyacrylic acid aqueous solution with the concentration of 0.005-0.02 mol/L;
(2) preparing a metal salt solution with the concentration of 0.1-3 mol/L;
(3) and adding the metal salt solution into the polyacrylic acid solution, and reacting for 3-6h to obtain a mixed solution, namely the polyacrylic acid/metal colloid particle film-forming material.
Preferably, the molar ratio of the polyacrylic acid to the metal salt in the mixed solution is 1:150 to 1: 20.
Preferably, the metal salt solution is an aqueous solution of a zinc salt, a calcium salt or a cerium salt.
Preferably, the pH value of the polyacrylic acid aqueous solution is 3.5-6.
Preferably, the pH of the metal salt solution is 3.5 to 6.
Preferably, the molecular weight of the polyacrylic acid is 3000-.
Preferably, in the step (3), the metal salt solution is placed in a constant pressure dropping funnel, and is dropwise added into the polyacrylic acid solution at a constant speed while stirring.
The invention has the action principle that polyacrylic acid can be ionized to generate a large amount of-COO-groups by adjusting the pH value of a polyacrylic acid solution, the-COO-groups can form polyacrylic acid/metal aggregates by electrostatic adsorption reaction with gradually added metal cations, the aggregates formed preliminarily can be further assembled with the reaction to finally form polyacrylic acid/metal colloid particles, and the polyacrylic acid film-forming material doped with the polyacrylic acid/metal colloid particles which are uniformly and stably dispersed can be obtained by controlling the reaction conditions.
The polyacrylic acid/metal colloid particle film-forming material prepared by the invention is applied to the pretreatment of the surface of steel, and a polyacrylic acid pretreatment film layer doped with colloid particles is formed on the surface of the steel, and the preparation method comprises the following specific steps: and soaking the deoiled and washed cold-rolled steel plate in the related polyacrylic acid/metal colloid particle film-forming material solution, taking out and airing, and spontaneously forming a polyacrylic acid pretreatment film layer doped with colloid particles on the metal plate.
The invention has the beneficial effects that: compared with the prior art, the polyacrylic acid/metal colloid particle film forming material is synthesized in situ by using a technical means of colloid particle doping, the film forming performance of the polyacrylic acid is effectively improved through nano modification, the quality of a formed pretreatment film layer is improved, and the adhesive force and the corrosion resistance of the film forming material are improved; the method specifically comprises the following steps:
(1) the water-soluble polymer polyacrylic acid is an environment-friendly polymer, and metal ions for preparing colloidal particles select non-toxic or low-toxicity metal inorganic salts such as zinc, calcium or cerium and the like as raw materials, so that the environment is friendly;
(2) the synthesis method is easy to synthesize and low in cost, and the synthesis method utilizes the electrostatic adsorption reaction between carboxyl anions and metal cations to carry out in-situ synthesis, has mild reaction conditions, and does not need extra harsh reaction conditions; the raw materials are all common raw materials with low price.
(3) The compactness and the roughness of the film layer are obviously improved, and the adhesive force and the corrosion resistance are improved; the single organic film layer has obvious defects due to internal stress in the forming process, the corrosion resistance of the film layer is influenced, the single organic film layer is mainly absorbed to form a film by self-assembly, the film layer is thin, the roughness is low, and the adhesive force performance of the film layer is influenced; through the method, as can be seen from fig. 2, the polyacrylic acid film-forming material doped with colloidal particles synthesized by the method contains a large number of particles with the diameter of 100-200nm, and the particles can be doped into the formed pretreatment film layer, so that on one hand, the stress of the film layer is eliminated due to the doping of the particles, and the defects of the film layer are reduced; on the other hand, the roughness of the film layer can be obviously improved, the contact area between the pretreatment film layer and the external coating layer is increased, and the paint film adhesive force performance of the coating is improved; as shown in FIG. 3, the compactness and the roughness of the pre-treatment film layer prepared by the polyacrylic acid/metal colloid particle film-forming material synthesized in the invention are obviously improved.
Drawings
FIG. 1 is a diagram illustrating the synthetic mechanism of the polyacrylic acid/metal colloid particle film-forming material of the present invention;
FIG. 2 is a transmission electron microscope image of a polyacrylic acid/metal colloid particle film-forming material of the present invention;
FIG. 3 is a scanning electron microscope image of a pre-treated film layer prepared from the polyacrylic acid/metal colloid particle film-forming material of the present invention;
FIG. 4 shows the results of adhesion and corrosion resistance tests of the pre-treated film of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
The invention is further illustrated by the following specific examples in combination with the accompanying drawings.
Example 1:
the preparation method of the polyacrylic acid/metal colloid particle film-forming material comprises the following steps:
(1) preparing 20ml of polyacrylic acid aqueous solution with the concentration of 0.005 mol/L;
(2) preparing 20ml of zinc nitrate solution with the concentration of 0.1 mol/L;
(3) and (2) placing the zinc nitrate solution into a constant-pressure dropping funnel, dropwise adding the zinc nitrate solution into the polyacrylic acid solution at a constant speed while stirring, and reacting for 3 hours to obtain a mixed solution, namely the polyacrylic acid/zinc colloid particle film-forming material.
The pH of the aqueous polyacrylic acid solution described in this example was 5.
The pH of the zinc nitrate solution described in this example was 5.
The polyacrylic acid described in this example had a molecular weight of 3000.
As shown in figure 1, polyacrylic acid can be ionized to generate a large number of-COO-groups by adjusting the pH value of a polyacrylic acid solution, the-COO-groups can form a polyacrylic acid/metal aggregate through electrostatic adsorption reaction with gradually added metal cations, the initially formed aggregate can be further assembled with the reaction to finally form polyacrylic acid/metal colloid particles, and the polyacrylic acid film-forming material doped with the polyacrylic acid/metal colloid particles can be obtained in a uniform and stable dispersion manner by controlling the reaction conditions.
As can be seen from FIG. 2, the polyacrylic acid film-forming material doped with colloidal particles synthesized by the present invention contains a large number of particles with a diameter of 100-200nm, and these particles can be doped into the formed pre-treatment film layer, on one hand, the stress of the film layer is eliminated due to the doping of the particles, and the defects of the film layer are reduced; on the other hand, the roughness of the film layer can be obviously improved, the contact area between the pretreatment film layer and the external coating layer is increased, and the paint film adhesive force performance of the coating is improved; as shown in FIG. 3, the compactness and the roughness of the pre-treatment film layer prepared by the polyacrylic acid/metal colloid particle film-forming material synthesized by the invention are obviously improved.
Example 2:
the preparation method of the polyacrylic acid/metal colloid particle film-forming material comprises the following steps:
(1) preparing 20ml of polyacrylic acid aqueous solution with the concentration of 0.01 mol/L;
(2) preparing 20ml of calcium nitrate solution with the concentration of 0.35 mol/L;
(3) and (3) placing the calcium nitrate solution into a constant-pressure dropping funnel, dropwise adding the calcium nitrate solution into the polyacrylic acid solution at a constant speed while stirring, and reacting for 3 hours to obtain a mixed solution, namely the polyacrylic acid/calcium colloid particle film-forming material.
The pH of the aqueous polyacrylic acid solution described in this example was 5.
The pH of the calcium nitrate solution described in this example was 5.
The polyacrylic acid described in this example had a molecular weight of 5000.
Example 3:
the preparation method of the polyacrylic acid/metal colloid particle film-forming material comprises the following steps:
(1) preparing 20ml of polyacrylic acid aqueous solution with the concentration of 0.005 mol/L;
(2) preparing 20ml of cerium nitrate solution with the concentration of 0.7 mol/L;
(3) and (3) placing the cerium nitrate solution in a constant-pressure dropping funnel, dropwise adding the cerium nitrate solution into the polyacrylic acid solution at a constant speed while stirring, and reacting for 3 hours to obtain a mixed solution, namely the polyacrylic acid/cerium colloidal particle film-forming material.
The pH of the aqueous polyacrylic acid solution described in this example was 5.
The pH of the cerium nitrate solution described in this example was 5.
The polyacrylic acid described in this example had a molecular weight of 10000.
Example 4:
the polyacrylic acid/zinc colloid particle film forming material aqueous solution synthesized in example 1 is selected as a film forming agent, a pretreatment film layer is prepared on the surface of a cold-rolled steel plate, the pretreatment film layer is subjected to electrostatic powder spraying coating, and the adhesion and the corrosion resistance of the prepared pretreatment film layer are evaluated by using an impact test and a neutral salt spray test. The experimental result is shown in fig. 4, the front and back surfaces of the coated coating have no radioactive cracks after being subjected to hammer peening tests of 50 and 80cm hammers, and the scribed part has no obvious extension after being subjected to salt spray tests for 500 hours, so that the pretreatment film prepared by the invention has excellent adhesive force and corrosion resistance.
The above embodiments are only specific examples of the present invention, and the protection scope of the present invention includes but is not limited to the product forms and styles of the above embodiments, and any suitable changes or modifications made by those skilled in the art according to the claims of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of a polyacrylic acid/metal colloid particle film-forming material is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing polyacrylic acid aqueous solution with the concentration of 0.005-0.02 mol/L;
(2) preparing a metal salt solution with the concentration of 0.1-3 mol/L;
(3) and adding the metal salt solution into the polyacrylic acid solution, and reacting for 3-6h to obtain a mixed solution, namely the polyacrylic acid/metal colloid particle film-forming material.
2. The method for preparing a polyacrylic acid/metal colloidal particle film-forming material according to claim 1, wherein: the molar ratio of the polyacrylic acid to the metal salt in the mixed solution is 1:150-1: 20.
3. The method for preparing a polyacrylic acid/metal colloidal particle film-forming material according to claim 1, wherein: the metal salt solution is an aqueous solution of zinc salt, calcium salt or cerium salt.
4. The method for preparing a polyacrylic acid/metal colloidal particle film-forming material according to claim 1, wherein: the pH value of the polyacrylic acid aqueous solution is 3.5-6.
5. The method for preparing a polyacrylic acid/metal colloid particle film-forming material as claimed in claim 1, wherein the molecular weight of the polyacrylic acid is 3000-20000.
6. The method for preparing a polyacrylic acid/metal colloidal particle film-forming material according to claim 1, wherein: and (3) placing the metal salt solution into a constant-pressure dropping funnel, and dropwise adding the metal salt solution into the polyacrylic acid solution at a constant speed while stirring.
7. A polyacrylic acid/metal colloid particle film-forming material is characterized in that: the polyacrylic acid/metal colloid particle film-forming material is prepared by the preparation method of the polyacrylic acid/metal colloid particle film-forming material in any one of claims 1 to 6.
8. The polyacrylic acid/metal colloid particle film-forming material according to claim 7, characterized in that: the polyacrylic acid/metal colloidal particle film-forming material is applied to the pretreatment of the surface of steel, and a polyacrylic acid pretreatment film layer doped with colloidal particles is formed on the surface of the steel, and the method comprises the following specific steps: and soaking the deoiled and washed cold-rolled steel plate in the related polyacrylic acid/metal colloid particle film-forming material solution, taking out and airing, and spontaneously forming a polyacrylic acid pretreatment film layer doped with colloid particles on the metal plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910934469.5A CN110607102A (en) | 2019-09-29 | 2019-09-29 | Polyacrylic acid/metal colloid particle film forming material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910934469.5A CN110607102A (en) | 2019-09-29 | 2019-09-29 | Polyacrylic acid/metal colloid particle film forming material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110607102A true CN110607102A (en) | 2019-12-24 |
Family
ID=68893895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910934469.5A Pending CN110607102A (en) | 2019-09-29 | 2019-09-29 | Polyacrylic acid/metal colloid particle film forming material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110607102A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225836A (en) * | 2020-10-16 | 2021-01-15 | 四川大学 | Metal ion transfer carrier and preparation method and application thereof |
| CN116285462A (en) * | 2023-03-17 | 2023-06-23 | 齐鲁工业大学(山东省科学院) | Preparation method of low-surface treatment coating based on lamellar carbon nano-sheet |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603174A (en) * | 2009-07-28 | 2009-12-16 | 武汉钢铁(集团)公司 | Non-chromium pretreating agent for color coated steel plate |
| CN102851660A (en) * | 2012-09-29 | 2013-01-02 | 西安建筑科技大学 | Phosphorus-free and chromium-free passive film-forming solution for steel surfaces and usage method thereof |
| CN104277173A (en) * | 2014-10-30 | 2015-01-14 | 东南大学 | Polyacrylic acid metal salt/boron oxide material as well as preparation method and application thereof |
| CN108753164A (en) * | 2018-06-20 | 2018-11-06 | 湖南辰砾新材料有限公司 | A kind of steel anti-corrosive coating and preparation method thereof |
-
2019
- 2019-09-29 CN CN201910934469.5A patent/CN110607102A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603174A (en) * | 2009-07-28 | 2009-12-16 | 武汉钢铁(集团)公司 | Non-chromium pretreating agent for color coated steel plate |
| CN102851660A (en) * | 2012-09-29 | 2013-01-02 | 西安建筑科技大学 | Phosphorus-free and chromium-free passive film-forming solution for steel surfaces and usage method thereof |
| CN104277173A (en) * | 2014-10-30 | 2015-01-14 | 东南大学 | Polyacrylic acid metal salt/boron oxide material as well as preparation method and application thereof |
| CN108753164A (en) * | 2018-06-20 | 2018-11-06 | 湖南辰砾新材料有限公司 | A kind of steel anti-corrosive coating and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112225836A (en) * | 2020-10-16 | 2021-01-15 | 四川大学 | Metal ion transfer carrier and preparation method and application thereof |
| CN112225836B (en) * | 2020-10-16 | 2022-03-22 | 四川大学 | Metal ion transfer carrier and preparation method and application thereof |
| CN116285462A (en) * | 2023-03-17 | 2023-06-23 | 齐鲁工业大学(山东省科学院) | Preparation method of low-surface treatment coating based on lamellar carbon nano-sheet |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717930B (en) | Environment-friendly nano water-based silane treatment agent capable of improving anti-corrosion performance of metal surface | |
| CN107761088B (en) | Corrosion-resistant neutral chromium-free coating agent and preparation method thereof | |
| CN110607102A (en) | Polyacrylic acid/metal colloid particle film forming material and preparation method and application thereof | |
| JP5280254B2 (en) | Self-lubricating galvanized metal material using a composition containing silica sol | |
| KR20100050541A (en) | Pretreatment compositions and methods for coating a metal substrate | |
| CN101258203A (en) | Coat-forming corrosion prentative and process for its electroless application | |
| CN108300302B (en) | Metal surface silane treating agent and preparation method thereof | |
| CN109609937B (en) | Method for preparing composite phosphating film by doping inorganic nanoparticles | |
| CN106833044A (en) | A kind of aqueous environment protection metal anti-corrosive paint and preparation method thereof | |
| Li et al. | Synthesis of stabilized dispersion covalently-jointed SiO2@ polyaniline with core-shell structure and anticorrosion performance of its hydrophobic coating for Mg-Li alloy | |
| CN103183990B (en) | Environment-friendly water-based anticorrosive paint and preparation method thereof | |
| CN111961412A (en) | Polysilazane modified epoxy single-component anticorrosive coating slurry, coating and preparation method | |
| Liu et al. | Robust Rare‐Earth‐Containing Superhydrophobic Coatings for Strong Protection of Magnesium and Aluminum Alloys | |
| CN109023335A (en) | A kind of metal material surface conversion film at film liquid and application thereof | |
| CN102534593A (en) | Resin/silane compounded passivation liquid for galvanized coil steel and preparation method of resin/silane compounded passivation liquid | |
| CN1311098C (en) | Method for making enamel steel plate | |
| CN114539877B (en) | Anticorrosion water-based epoxy coating based on divalent zinc ions and phytic acid modified graphene oxide and preparation method thereof | |
| CN101643621B (en) | Polyester heavy-duty anticorrosive coating with polyaniline-modified glass flakes, and preparation method thereof | |
| CN106835093A (en) | A kind of Q types POSS modified metal surface pretreating reagent and preparation method thereof, application | |
| CN106521471A (en) | Aluminum alloy surface environment-friendly film-forming agent and preparation method thereof | |
| CN1256302C (en) | Sintered metal powder coating material and method of preparing metal ceramic anti corrosive coating | |
| CN112029314A (en) | Nano-filler and preparation method and application thereof | |
| CN111777917A (en) | Preparation method of modified etched basalt scale/epoxy resin composite coating | |
| CN114481012B (en) | Multielement alloy co-permeation agent for steel member and corrosion prevention process thereof | |
| CN111074255A (en) | Metal surface pretreatment agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191224 |
|
| RJ01 | Rejection of invention patent application after publication |